WO2006088164A1

WO2006088164A1 - Microparticle enclosing resin component and use thereof

Info

Publication number: WO2006088164A1
Application number: PCT/JP2006/302895
Authority: WO
Inventors: Masayoshi Okubo; Hideto Minami; Toyoko Suzuki
Original assignee: National University Corporation Kobe University
Priority date: 2005-02-17
Filing date: 2006-02-17
Publication date: 2006-08-24
Also published as: JP2006225521A

Abstract

A process for producing hardener-enclosing epoxy resin microparticles, comprising the step of dispersing in an aqueous solution of dispersion stabilizer a mixture containing an epoxy resin, an epoxy resin hardener and an auxiliary solvent or auxiliary polymer having the following properties wherein the ratio, in terms of chemical equivalent ratio, of hardener to epoxy resin is in the range of 2 to 15; and the subsequent step of hardening the epoxy resin. The auxiliary polymer or auxiliary solvent has low compatibility with the epoxy resin resulting from hardening of the epoxy resin with the hardener, and the interfacial tension between auxiliary polymer or auxiliary solvent and water, Ϝp mN/m, and the interfacial tension between hardened epoxy resin and water, Ϝq mN/m, satisfy the relationship Ϝp≥Ϝq.

Description

Resin component-containing fine particles and use thereof

Technical field

[0001] The present invention relates to a curing agent-encapsulated fine particle in which a curing agent for epoxy resin is encapsulated in a shell made of a cured epoxy resin, a simple manufacturing method thereof, and a one-pack type using the curing agent-encapsulated fine particle The present invention relates to an epoxy resin adhesive composition.

[0002] The present invention also provides fine particles in which a polyisocyanate or an active hydrogen compound as a constituent component of these isocyanate resins is encapsulated in a shell having isocyanate strength such as polyurethane, polyurea, and polythiourethane. The present invention relates to a simple production method, and a one-component isocyanate complex resin composition using the polyisocyanate resin component-encapsulating fine particles.

Background art

[0003] Epoxy resin is reacted with a curing agent such as amines and acid anhydrides to form an insoluble and infusible cured product having a three-dimensional network structure. Cross-linked cured epoxy resin has excellent adhesion, electrical insulation, chemical resistance, heat resistance, etc., so it is widely used for electronic parts, civil engineering / architecture, space, aircraft, vehicles, and sports equipment. Used as an adhesive for applications.

[0004] Conventionally used epoxy resin adhesives are two-pack adhesives in which epoxy resin and curing agent are filled in separate containers and mixed together at the time of use to cure epoxy resin It is an agent. Two-part adhesives may not be preferred because they are cumbersome to mix during use.

[0005] As a one-pack type epoxy resin adhesive that does not require such labor, Patent Document 1 describes: (A) epoxy resin; (B) glass transition point of -30 ° C or less (meta) A copolymer of an acrylate polymer and a Z or gen polymer core, a (meth) acrylate monomer and a radically polymerizable unsaturated carboxylic acid monomer, having a glass transition point of 70 Disclosed is an epoxy resin adhesive composition comprising a shell having a strength higher than ° C and ion-crosslinked by adding metal ions; and (C) a hard-capsule type epoxy resin hardener. is doing. The microcapsule-type curing agent described in Patent Document 1 is heated by microcapsule. The resin is melted and the curing agent and epoxy resin are reacted.

[0006] Patent Document 2 discloses a one-component conductive adhesive in which a microcapsule type curing agent in which an amine-based curing agent is encapsulated in a microcapsule composed of conductive particles, epoxy resin, and thermoplastic resin. An agent is disclosed. When using an adhesive, for example, the capsule is melted by applying a temperature of 100 ° C., and the epoxy resin and the amine curing agent are reacted.

However, these conventional one-pack type epoxy resin adhesives are troublesome in encapsulating the curing agent.

[0008] Polyisocyanates react with active hydrogen compounds such as polyols, polyamines, and polythiols to insoluble and insoluble three-dimensional network structures such as polyurethane resins, polyurethane resins, and polythiourethane resins. Give melted grease.

[0009] Since the cohesive energy of the bond formed between the isocyanate group and the active hydrogen compound is relatively large, isocyanate resin is used as an adhesive. In addition, the adhesive layer made of isocyanate resin is not only strong in adhesion but also excellent in heat resistance, water resistance, impact resistance and the like. Furthermore, the polarity, crystallinity, softness, glass transition point, etc. can be freely changed by selecting polyisocyanate or active hydrogen compound, so the structure can be designed to suit the properties of the adherend. .

[0010] Isocyanate resin adhesives include a one-component type and a two-component type. The two-component type cures by mixing an isocyanate component and an active hydrogen component on site. In addition, the one-component type includes, for example, a type of prepolymer having a polyisocyanate attached to the end of a polyol, which is cured by reacting with moisture in the air, adsorbed water or active hydrogen groups on the surface of the adherend, The mixture of the isocyanate group of the polyisocyanate blocked with a blocking agent and the active hydrogen compound also becomes a mixture force, and when heated to a high temperature, the blocking agent is released and the polyisocyanate is activated to form an active hydrogen compound. The type of reaction is known. The one-pack type is the mainstream because it is easy to work and does not cause incorrect mixing ratios on site.

[0011] However, the moisture-curable one-component type is inferior in storage stability because it is sensitive to moisture, and the one-component type sealed with a blocking agent currently has a dissociation temperature of 100 ° C or higher. However, it has been developed! Patent Document 1: JP-A-8-100163

Patent Document 2: JP-A-5-47212

Disclosure of the invention

Problems to be solved by the invention

[0012] A first object of the present invention is a curing agent-encapsulated fine particle that can be used as a curing agent for a one-pack type epoxy resin adhesive, which can be easily produced, a simple method for producing the fine particle, and the fine particle. It is to provide a one-pack type epoxy resin adhesive composition using

[0013] The second object of the present invention is to provide a practical one-component isocyanate complex resin composition excellent in storage stability, isocyanate resin component-encapsulated fine particles that can be used as a component of the composition, and It is to provide a simple method for producing the fine particles.

Means for solving the problem

[0014] In order to solve the above problems, the present inventors have conducted research and obtained the following knowledge.

(0 In the dispersion stabilizer aqueous solution, epoxy resin, epoxy resin curing agent, auxiliary polymer or auxiliary solvent having the following properties, and the mixing ratio of the curing agent is the chemical equivalent ratio for epoxy resin. After the mixture of 2 to 15 is dispersed, the epoxy resin is cured, and fine particles in which a curing agent is enclosed in a shell made of the cured epoxy resin can be easily obtained.

[0015] Auxiliary polymer or auxiliary solvent: Curing process obtained by reaction of epoxy resin and curing agent. Low compatibility with poxy resin and interface tension between auxiliary polymer or auxiliary solvent and water A polymer or solvent that satisfies the condition of γ ^と ≥ γ ¹¹ in the relationship between ( _Ί ^P ) (mN / m) and the interfacial tension (γ ^q ) (mN / m) between the cured epoxy resin and water

This composition containing fine particles and epoxy resin can be used in combination with epoxy resin and curing agent if the shell is broken by a stimulus such as pressing or grinding during use, or if the curing agent is released by applying heat. Can be used as a one-part adhesive because the epoxy resin is cured by contact.

(ii) An aqueous dispersion stabilizer solution contains a polyisocyanate and an active hydrogen compound selected from the group consisting of polyol, polyamine, and polythiol power, and the active hydrogen compound has a mixing ratio of the polyisocyanate. In contrast, a mixture having a chemical equivalent ratio of 2 to 25 was dispersed. Thereafter, polyisocyanate and an active hydrogen compound are subjected to a polyaddition reaction to easily obtain fine particles in which the active hydrogen compound is enclosed in a shell made of a cured isocyanate resin.

(iii) When the mixture to be dispersed in the aqueous dispersion stabilizer further contains an auxiliary polymer or auxiliary solvent having the following properties, the polyisocyanate reacts with the active hydrogen compound in the mixture. In order to promote phase separation of the polyisocyanate and active hydrogen compound and the isocyanate resin when the isocyanate resin is adsorbed on the interface with water, the shell is formed from the isocyanate resin. In addition, fine particles containing a polyisocyanate and an active hydrogen compound can be easily obtained. For this reason, when an auxiliary polymer or an auxiliary solvent is used, the polyisocyanate and the active hydrogen compound can be selected from a wide range of V and range forces.

[0016] Auxiliary polymer or auxiliary solvent: low compatibility with isocyanate resin obtained by reaction of polyisocyanate and active hydrogen compound, and interfacial tension between auxiliary polymer or auxiliary solvent and water ( γ ^x) (mN / m) and Isoshianeto榭脂and interfacial tension between water (gamma ^y) (in relation to the mN / m), satisfying the polymer or solvent ^{^γ} χ ≥ γ Υ

(iv) In the processes of (ii) and (iii) above, the polyisocyanate is excessive with respect to the active hydrogen compound, that is, the compounding ratio of the polyisocyanate is 2 in terms of a chemical equivalent ratio with respect to the active hydrogen compound. In the case of ˜25, fine particles in which polyisocyanate is encapsulated in a shell made of isocyanate resin can be easily obtained.

(V) A composition containing fine particles encapsulating active hydrogen compound and polyisocyanate can be used if the shell is broken by irritation such as pressing or grinding at the time of use, or the active hydrogen compound is released by applying heat. Since polyisocyanate and active hydrogen compound react and harden when contacted, it can be used as a one-part adhesive.

[0017] Similarly, a composition containing polyisocyanate-encapsulated fine particles and an active hydrogen compound can be obtained by destroying the shell by pressing or heating to release the polyisocyanate and releasing the polyisocyanate. Can be used as a one-part adhesive because it contacts and reacts to cure.

[0018] The present invention has been completed based on the above findings, and provides the following curing agent-encapsulated fine particles and the like. [0019] Item 1. Shell and hollow part force A hollow part of a hollow fine particle having an epoxy resin hardener encapsulated in a hollow part, wherein the shell is substantially the same kind as the encapsulated hardener. Curing agent-encapsulated fine particles comprising a cured epoxy resin obtained by a reaction between a curing agent and epoxy resin.

[0020] Item 2. The fine particles according to Item 1, wherein the epoxy resin is a bi- to hexafunctional epoxy resin.

Item [0021] Item 3. Strength of inclusion of curing agent The fine particle according to Item 1, which is 50 to 500% by weight based on the shell.

[0022] Item 4. The fine particle according to Item 1, wherein the average particle size is 0.1 to 50 m.

[0023] Item 5. The fine particle according to Item 1, wherein the volume ratio R of the curing agent-containing portion, calculated according to the following formula, is 10 to 80%.

[0024] R (%) = (rh / rp) ³ X 100

(Wherein rh is the radius of the hardener-containing portion of the fine particles, and rp is the radius of the fine particles.) Item 6. The fine particles according to Item 1, wherein the crushing limit load is 1 to: LOOmN.

Item 7. A curing agent for a one-pack type epoxy resin adhesive containing the fine particles according to Item 1.

Item 8. Use of the fine particles according to Item 1 as a curing agent for a one-pack type epoxy resin adhesive.

[0027] Item 9. A method for producing fine particles in which a hollow portion of a hollow fine particle having a shell and a hollow partial force encapsulates an epoxy resin hardener,

The aqueous solution of the dispersion stabilizer contains epoxy resin, epoxy resin hardener, auxiliary polymer or auxiliary solvent having the following properties, and the compounding ratio of the hardener is 2 in terms of chemical equivalent to epoxy resin. A production method comprising a first step of dispersing the mixture of ˜15 and a second step of curing the epoxy resin.

[0028] Auxiliary polymer or auxiliary solvent: Curing process obtained by reaction of epoxy resin and curing agent. Low compatibility with poxy resin and interface tension between auxiliary polymer or auxiliary solvent and water A polymer or solvent that satisfies the condition of γ ^と ≥ γ ¹¹ in the relationship between ( _Ί ^P ) (mN / m) and the interfacial tension (γ ^q ) (mN / m) between the cured epoxy resin and water

[0029] Item 10. The method according to Item 9, wherein the epoxy resin is a bi- to 6-functional epoxy resin.

[0030] Item 11. A one-pack type epoxy resin adhesive comprising the fine particles according to item 1 and an epoxy resin Agent composition.

[0031] Item 12. A step of placing the composition according to Item 11 between a pair of adherends, a step of releasing the curing agent from the fine particle sheller by pressing the adherends, an epoxy resin, A method for adhering an adherend, comprising a step of cross-linking a curing agent and adhering the adherend.

[0032] Item 13. The step of placing the fine particles according to Item 1 and the epoxy resin in a mixed state between a pair of adherends, and pressing the adherends together to release the fine particle shell force curing agent. A method of bonding an adherend, comprising a step of cross-linking the epoxy resin and the curing agent to bond the adherends.

[0033] Item 14. A fine particle in which an active hydrogen compound or polyisocyanate selected from the group consisting of polyol, polyamine, and polythiol force is encapsulated in a hollow portion of a hollow fine particle having a shell and a hollow partial force. In particular, isocyanate resin component-encapsulated fine particles comprising a isocyanate resin obtained by polyaddition reaction of the same type of component as the encapsulated component with polyisocyanate or the active hydrogen compound.

Item 15. The fine particle according to Item 14, wherein the inclusion force of the isocyanate component is 50 to 1500% by weight relative to the shell.

[0035] Item 16. The fine particle according to Item 14, wherein the average particle size is 0.1 to 50 / ζ πι.

[0036] Item 17. The fine particle according to Item 14, wherein the volume ratio R of the isocyanate-containing resin component-containing portion, calculated according to the following formula, is 30 to 95%.

[0037] R (%) = (rh / rp) ³ X 100

(Where rh is the radius of the isocyanate-containing component of the fine particles and rp is the radius of the fine particles.)

[0038] Item 18. The fine particle according to Item 14, wherein an active hydrogen compound selected from the group consisting of a polyol, a polyamine, and a polythiol force is included.

[0039] Item 19. The fine particle according to Item 14, wherein the polyisocyanate is encapsulated.

[0040] Item 20. A one-component isocyanate resin component comprising the fine particles according to Item 14.

[0041] Item 21. Use of the fine particles according to Item 14 as a one-component isocyanate resin adhesive component.

[0042] Item 22. In the hollow portion of the hollow fine particle comprising a shell and a hollow portion, an isocyanate is added. A method for producing fine particles encapsulating a rosin component,

A mixture of a polyisocyanate and an active hydrogen compound selected from the group consisting of polyol, polyamine, and polythiol in an aqueous dispersion stabilizer solution, wherein the active hydrogen compound is mixed in a polyisocyanate. A first step of dispersing a mixture having a chemical equivalent ratio of 2 to 25 or a polyisocyanate mixture ratio of 2 to 25 in terms of a chemical equivalent ratio to the active hydrogen compound, and a polyisocyanate And a second step of subjecting the active hydrogen compound and the active hydrogen compound to a double caloric reaction.

[0043] Item 23. The method according to Item 22, wherein the mixture dispersed in the aqueous solution of the dispersion stabilizer contains an auxiliary polymer or auxiliary solvent having the following properties in addition to the polyisocyanate and the active hydrogen compound. .

[0044] Auxiliary polymer or auxiliary solvent: low compatibility with isocyanate resin obtained by polyaddition reaction of polyisocyanate and active hydrogen compound, and between auxiliary polymer or auxiliary solvent and water interfacial tension ^{(γ x) (mN / m} ) and Isoshianeto榭脂and interfacial tension between water ^{(γ y) (mN / m} ) and the related Nio Te, satisfies the condition polymers ^γ χ ≥ γ ^y Or solvent

[0045] Item 24. A one-component polyurethane adhesive composition comprising the fine particles according to Item 18 and a polyisocyanate.

[0046] Item 25. A one-component polyurethane adhesive composition comprising the fine particles according to Item 19 and an active hydrogen compound selected from the group consisting of polyols, polyamines, and polythiols.

Item 26. A step of placing the composition according to Item 24 between a pair of adherends, a step of releasing the active hydrogen compound from the fine particle sheller by pressing the adherends, and active hydrogen A method for adhering an adherend comprising the step of subjecting a compound and a polyisocyanate to a polyaddition reaction to adhere between the adherends.

[0048] Item 27. A step of mixing the fine particle according to Item 18 and a polyisocyanate between a pair of adherends, and releasing the active hydrogen compound from the fine particle sheller by pressing the adherends together. And a method of adhering the adherends by subjecting the active hydrogen compound and the polyisocyanate to a polyaddition reaction.

[0049] Paragraph 28. A step of placing the composition according to Paragraph 25 between a pair of adherends, a step of releasing the fine shell strength polyisocyanate by pressing the adherends together, A method for adhering an adherend, comprising a step of subjecting the adsorbate to a polyaddition reaction between a sulfonate and an active hydrogen compound.

[0050] Item 29. A step of mixing the fine particles according to Item 19 and an active hydrogen compound between a pair of adherends, and a step of releasing the fine particle shell force polyisocyanate by pressing the adherends together. And a step of adhering the adherends by polyaddition reaction of polyisocyanate and active hydrogen compound.

The invention's effect

[0051] The curing agent-encapsulated fine particles of the present invention can be used as a curing agent that is combined with an epoxy resin to form a one-pack type epoxy resin adhesive composition. When this adhesive is used, it breaks the fine particle shell by stimuli such as pressing or grinding, or when heat is applied above the glass transition temperature of the shell layer, the internal curing agent tends to diffuse and the curing agent is used. Can be released and react with epoxy resin.

[0052] Further, in the curing agent-encapsulated fine particles of the present invention, since the shell also has a cured epoxy resin layer strength or is mainly composed of a cured epoxy resin, the component derived from the shell remaining in the cured adhesive is an impurity. Not. For this reason, the adhesive strength is not reduced by impurities, and the transparency is greatly improved.

[0053] According to the method of the present invention, the dispersion containing the epoxy resin and the curing agent is dispersed in the dispersion stabilizer aqueous solution, and then the epoxy resin is cured by a simple operation. Fine particles in which a curing agent is enclosed in a shell made of cured epoxy resin are obtained.

[0054] When the inclusion component is a polyisocyanate, the isocyanate-containing resin-encapsulated fine particles of the present invention can be blended with an active hydrogen compound to form a one-component isocyanate resin-adhesive composition. When the encapsulated component is an active hydrogen compound, it can be blended with a polyisocyanate to form a one-pack type isocyanato resin adhesive composition.

[0055] In use, the one-component type isocyanate isocyanate resin breaks the fine particle shell by a stimulus such as pressing or grinding, or when heat is applied to raise the temperature above the glass transition temperature of the shell layer. The released component can be reacted with the other component.

[0056] The isocyanate-encapsulated component-containing fine particles of the present invention have an isocyanate shell. Since it consists of a toe resin layer or mainly this resin, the components derived from the shell remaining in the cured adhesive do not become impurities. As a result, the adhesive strength is not reduced by impurities and the transparency is greatly improved.

[0057] Further, according to the method of the present invention, after a mixture containing a polyisocyanate and an active hydrogen compound is dispersed in an aqueous dispersion stabilizer solution, a simple operation of reacting the two is practical. In addition, fine particles in which a polyisocyanate or an active hydrogen compound is encapsulated in a shell made of isocyanate resin are obtained.

BEST MODE FOR CARRYING OUT THE INVENTION

[0058] Hereinafter, the present invention will be described in detail.

m Stone Phrases, fine particles ¾¾

The production method of the present invention is a method for producing fine particles in which a hollow part of a hollow fine particle having a shell and a hollow partial force is encapsulated with a curing agent of epoxy resin. This method includes a first step in which a mixture containing the following (a) to (c) is dispersed in an aqueous dispersion stabilizer solution; and a second step in which the epoxy resin is cured. This mixture contains a curing agent at a chemical equivalent ratio of about 2 to 15 with respect to the epoxy resin.

(a) Epoxy resin

(b) Curing agent for epoxy resin

(c) Low compatibility with cured epoxy resin obtained by crosslinking epoxy resin with a curing agent, and interfacial tension between auxiliary polymer or auxiliary solvent and water (γ P) ( mN / m), auxiliary polymer or solvent satisfying the condition of γ ^ γ ^{11 in} relation to the interfacial tension (γ ^q ) (mN / m) between the cured epoxy resin and water

Dispersion stabilizer

A dispersion stabilizer having a function of preventing droplets formed by dispersing a mixture of an epoxy resin, a curing agent, and an auxiliary polymer or an auxiliary solvent in water from coalescing can be used in a wide range. .

[0059] For example, polybulol alcohol, methylcellulose, ethylcellulose, polyacrylic acid, polyacrylimide, polyethylene oxide, poly (nodoxyoxystearic acid-methyl methacrylate-co-methacrylic acid) copolymer, etc. Molecular dispersion stabilizer, NOON Surfactants, anionic surfactants, amphoteric surfactants and the like. Among these, polymer dispersion stabilizers such as polyvinyl alcohol are preferable.

[0060] The amount of the dispersion stabilizer used can be selected from a wide range. Generally, 0.005 to 1 part by weight with respect to 1 part by weight of the mixture of epoxy resin, hardener, and auxiliary polymer or auxiliary solvent. It is preferably about 0.01 to 0.5 parts by weight.

[0061] Further, the concentration of the dispersion stabilizer in the aqueous solution of the dispersion stabilizer may be appropriately selected so that the droplets do not coalesce. In general, the concentration of the dispersion stabilizer aqueous solution is preferably adjusted to about 0.05 to 5% by weight, particularly about 0.1 to 2% by weight. Epoxy resin

The epoxy resin is preferably poorly water-soluble, but this requirement is usually satisfied.

[0062] The type of epoxy resin is not particularly limited, and a known compound having two or more epoxy groups in one molecule can be used. For example, phenphenols such as bisphenol A, bisphenol F, brominated bisphenol A, hydrogenated bisphenol A, bisphenol nore S, bisphenol nore AF, resorcinol, phenol novolak, cresolol novolak, etc. were epoxidized using epicro hydrin. Alcohol-based glycidyl ethers obtained by epoxidizing alcohols such as phenol-based glycidyl ether, butanediol, polyethylene glycol, and polypropylene glycol with epichlorohydrin; phthalic acid, synthetic fatty acids (such as dimer acid), etc. using epichlorohydrin And epoxidized glycidyl ester; glycidylamine obtained by epoxidizing aminophenol or aminocresol with epichlorohydrin.

[0063] In addition to the bifunctional epoxy resin having two epoxy groups, a polyfunctional epoxy resin having three or more epoxy groups can be used as the epoxy resin. When using hardener-containing fine particles as an adhesive component, it is possible to form a shell having a strength that can easily break the shell and hold the hardener for a long period of time. It is more preferable to use a 2-4 functional epoxy resin.

[0064] In addition, the epoxy resin is a liquid at room temperature because it has good workability in the first step of dispersing droplets containing epoxy resin when the fine particles are produced by the method of the present invention described later. thing Such epoxy resins include bisphenol A type diglycidyl ether, bisphenol F type diglycidyl ether, triglycidyl isocyanate, tetraglycidyl diaminophenol methane and the like. Bisphenol F-type diglycidyl ether and tetraglycidyl diaminophenylmethane are more preferred.

[0065] One type of epoxy resin can be used alone, or two or more types can be used in combination. The curing agent crosslinks and cures the epoxy resin in the droplets, and a wide variety of oil-soluble polyfunctional curing agents known as epoxy resin curing agents can be used.

[0066] Specifically, aliphatic mamines such as polymethylene diamine, polyether diamine, branched polymethylene diamine, methane diamine, aminoethylpiperazine, diaminocyclohexane, isophorone diamine; Amines, tetrachloro-p-xylylenediamine, diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, diaminophenylsulfone, benzidine, 4,4 'bis (tonoleidine), 4,4'-dithioaniline, dianidine , Aromatic amines such as methylene bis (chloroarine) and toluenediamine; phthalic anhydride derivatives, alkaleic anhydride, dodece-succinic anhydride, maleic anhydride-butyl ether copolymer, maleic anhydride-styrene copolymer , Chlorendic anhydride, pyromellitic anhydride, no water benzophenone Acid anhydrides such as tracarboxylic acid, ethylene glycol bistrimeritite, glycerin tristrimerite; polyphenols; polymercaptans; tertiary amines such as benzyldimethylamine, 2,4,6 trisdimethylaminomethylphenol; 2 —Imidazoles such as methyl imidazole and 2-ethyl 4-methylimidazole; acids such as aromatic sulfo-um salt and aromatic diazo-um salt; phenol resin; urea resin; melamine resin. One curing agent can be used alone, or two or more curing agents can be used in combination.

[0067] In particular, polyamines such as polyamines, acid anhydrides, polyphenols, and polymercaptans are preferred, and polyamines such as polyamines and polyphenols are preferred (especially aromatic diamines). ,.

[0068] Further, as a preferable combination of epoxy resin and hardener, a combination of bisphenol A type diglycidyl ether (for example, Epofix manufactured by Struth) and 4,4, -diaminodiphenylmethane, bisphenol A type Diglycidyl ether (eg oily shell Epoxy Coat 828), dodecamethylene diamine, bisphenol F-type glycidyl ether (Epoxy Coat 806, Epoxy Coat 806) and 3, 9 Panam-2,4,8,1 0-tetraoxaspiro [5 , 5] Undecane (Japan Epoxy Resin, Epicure RX-3), Bisphenol F-type glycidyl ether (Japan Epoxy Resin, Epicort 806) Z Tetraglycidyldiamineaminomethane (Japan Epoxy Resin, Epicort 604) And combinations with 3,9-dipropanamine-2,4,8,10-tetraoxaspiro [5,5] undecane (manufactured by Japan Epoxy Resin, Epicure RX-3).

[0069] The amount of the curing agent used is the chemical equivalent specific force between the epoxy resin and the curing agent. Epoxy resin: hardener = about 1 to 2 to 15, preferably about 3 to about L0, more preferably 4 It should be about ~ 8. The chemical equivalent ratio here is the ratio of the number of epoxy groups in the epoxy resin to the number of reactive functional groups in the curing agent. That is, in the method of the present invention, the amount of the curing agent may be determined so that the number of reactive functional groups of the curing agent is about 2 to 15 with respect to the number of epoxy groups of the epoxy resin.

[0070] As described above, by using an excessive amount of the curing agent relative to the epoxy resin, an excessive hardener that does not participate in shell formation is taken into the hollow portion in the shell. Moreover, if the amount of the curing agent used for the epoxy resin is too large, the epoxy resin is difficult to cure, but if it is within the above range, the shell formation by the curing of the epoxy resin is performed rapidly.

Auxiliary polymer

In the process of the present invention, an auxiliary polymer or Z and an auxiliary solvent are used. These should satisfy the requirements of (d) and (1) below.

(d) Low against cured epoxy resin obtained by reaction of epoxy resin and curing agent!ヽ Compatible.

(D In relation to the interfacial tension between the auxiliary polymer or auxiliary solvent and water (γ ^P ) (mN / m) and the cured epoxy resin and interfacial tension between the resin and water (γ ¹¹ ) (mN / m) , Γ ≥ ≥ γ ¹¹ is ^satisfied .

[0071] Specifically, as the auxiliary polymer and auxiliary solvent, those having a lower polarity than the cured epoxy resin obtained by crosslinking the epoxy resin with a curing agent can be used. In this specification, the compatibility of the auxiliary polymer and auxiliary solvent with the cured epoxy resin is measured by the following method. That is, a monomer component solution containing epoxy resin, which is a raw material of cured epoxy resin, auxiliary polymer or auxiliary solvent, and toluene if necessary in an appropriate weight ratio, is added with a curing agent (to epoxy resin). Add an equivalent chemical equivalent) to cause crosslinking reaction of epoxy resin in a nitrogen gas atmosphere at 70 ° C. This reaction is carried out in a quartz glass cell having an optical path length of 1 cm, and the light transmittance is measured over time when irradiated with light having a wavelength of 550 nm. As the concentration of the auxiliary polymer or auxiliary solvent is increased, the transmittance, which was about 100% at the beginning, rapidly decreases to near 0% when the crosslinking time elapses due to phase separation of the cured epoxy resin. In this case, the compatibility between the auxiliary polymer or auxiliary solvent and the cured epoxy resin decreases to nearly 0%, but the transmittance increases if the compatibility between the auxiliary polymer or auxiliary solvent and the cured epoxy resin is high. Almost never drops. In addition, the lower the compatibility between the auxiliary polymer or auxiliary solvent and the cured epoxy resin, the shorter the time from the start of curing until the decrease in transmittance occurs.

[0073] The auxiliary polymer or auxiliary solvent having a low compatibility with the cured epoxy resin and the auxiliary solvent has a crosslinking rate of about 1 to 20% when the transmittance is measured by the above method, preferably An auxiliary polymer or an auxiliary solvent in which the transmittance is reduced at about 1 to 10% can be mentioned.

[0074] Further, in the present invention, the interfacial tension is a value measured by a Duny platinum ring method defined in ASTM-971-50.

[0075] Although the auxiliary polymer and the auxiliary solvent are desirably soluble in the epoxy resin and the curing agent, this requirement is usually satisfied.

[0076] The auxiliary polymer and the auxiliary solvent satisfying the requirements of (d) and (1) promote phase separation between the epoxy resin and the curing agent and the cured epoxy resin obtained by crosslinking. In addition, epoxy resin is cross-linked into a cured epoxy resin in a mixture of epoxy resin, curing agent, auxiliary polymer or Z and auxiliary solvent, and the cured epoxy resin is adsorbed at the interface with water. In this case, the cured epoxy resin is more easily adsorbed at the interface with water than the auxiliary polymer or Z and auxiliary solvent, and as a result, fine particles having a shell made of the cured epoxy resin are obtained. At this time, as described above, the curing agent is more excessive than the epoxy resin. Because of the presence, excess curing agent is incorporated into the shell along with the auxiliary polymer or z and auxiliary solvent.

[0077] As the auxiliary polymer, for example, polystyrene, polymethyl methacrylate, polybutyl methacrylate and the like can be used. One auxiliary polymer can be used alone, or two or more auxiliary polymers can be used in combination. The combination of epoxy resin, curing agent and auxiliary polymer that satisfies the requirements of (d) and (D) is a force that can be easily selected by the method described above. For example, bisphenol F type diglycidyl ether and 3, 9 Panam-2,4,8,10-Tetraoxaspyro [5,5] undecane in combination with polymethyl methacrylate, bisphenol F-type glycidyl ether Z tetraglycidyl diaminophenol and 3, 9 Examples thereof include a combination of panamamine-2,4,8,10-tetraoxaspiro [5,5] undecane and polymethyl methacrylate.

[0078] As the auxiliary solvent, a solvent having about 12 to 16 carbon atoms that is liquid at room temperature can be used. Such solvents include linear and branched aliphatic hydrocarbon solvents such as dodecane, tridecane, tetradecane, pentadecane, hexadecane; cyclohexyl benzene, 1,2-dimethylnaphthalene, 1,3-dimethyl Aromatic hydrocarbon solvents such as naphthalene and 1,6-dimethylnaphthalene; ether solvents such as dibenzyl ether; triethyl acetyltaenoate, isoamyl benzoate, benzyl benzoate, isoamyl salicylate, benzyl salicylate, sulphur Examples include ester solvents such as diamyl acid, dibutyl tartrate, and jetyl phthalate; nitrogen-containing solvents such as dioctylamine, dicyclohexylamine, Ν, Ν-dibutylamine, triamylamine, and tri-η-ptyramine. Co-solvents can be used alone or in combination of two or more.

[0079] (d) and (A combination of an epoxy resin satisfying the requirements of D, a curing agent, and a cosolvent can be easily selected by the method described below. For example, bisphenol A type diglycidyl ether ( Strepus, Epofix) and 4,4, -diaminodiphenol methane and xylene, bisphenol A type diglycidyl ether (Oka Chemical Shell Epoxy, Epicoat 828) and the curing agent dodecamethylene diamide Examples include a combination of min and hexadecane.

[0080] When the auxiliary polymer is used, the amount used is not limited thereto. About 0.01 to 2 parts by weight, especially 0.02 per 1 part by weight of the total amount of the resin and curing agent

It is preferably about 0.1 parts by weight.

[0081] The amount of co-solvent used is not limited to this, but is about 0.1 to 5 parts by weight, especially 0 for the total amount of epoxy resin and curing agent of 1 part by weight. 5 to 2 parts by weight is preferred.

[0082] If the amounts of the auxiliary polymer and Z or auxiliary solvent used are in the above ranges, the shell is sufficiently formed and the content of the curing agent is not relatively reduced.

i process (¾ process)

In the present invention, an epoxy resin, a curing agent, and an auxiliary polymer or a mixture containing Z and an auxiliary solvent in the above-mentioned proportions are dispersed in an aqueous dispersion stabilizer solution, and a suspension crosslinking reaction is performed.

[0083] During the dispersion step, it is preferable that the curing agent, the auxiliary polymer or Z and the auxiliary solvent are dissolved in an epoxy resin to form a uniform solution. The temperature at the time of mixing is not particularly limited, and may be, for example, about O to 30 ° C.

[0084] The epoxy resin, curing agent, and auxiliary polymer or mixture of Z and auxiliary solvent thus obtained are dispersed in an aqueous solution of a dispersion stabilizer.

[0085] The homogeneous solution is preferably used in an amount of about 1 to 200 parts by weight, particularly about 10 to 100 parts by weight per 100 parts by weight of the aqueous dispersion stabilizer solution. It is not limited.

[0086] The dispersion method is not particularly limited, and a known method may be employed. Examples of such known dispersion methods include a method using a homogenizer and a dispersion method using mechanical shearing force such as a membrane emulsification method. The temperature condition during dispersion is not limited to this, but it may be about 0 to 30 ° C.

[0087] In the dispersion method exemplified above, the size of the droplets formed by dispersing the epoxy resin, the curing agent, and the auxiliary polymer or the mixture of Z and the auxiliary solvent is generally different from that of the monodisperse. A droplet having a particle size is mixed. Therefore, the hard-encapsulated fine particles finally obtained also have different particle sizes.

[0088] On the other hand, by selecting a dispersion method, the size of the droplets is made uniform, and monodispersed droplets are formed. It can also be obtained. As a method for obtaining such monodispersed droplets, for example, porous glass (

Examples thereof include a method of producing monodispersed droplets by a membrane emulsification method using SPG) and a seed swelling method (method described in JP-A-8-20604).

[0089] When such monodispersed liquid droplets having a uniform particle size are prepared, the finally obtained curing agent-containing fine particles are also monodispersed with a uniform particle size. Monodispersed hardener-encapsulated microparticles, when used as a one-part epoxy resin adhesive, have uniform fracture conditions, resulting in an adhesive with a uniform hardener concentration distribution and consequently uniform adhesive strength. .

[0090] Even in the case of V deviation, the average particle size of the droplets may be appropriately determined according to the desired average particle size of the hardener-encapsulating fine particles, but is generally about 0.1 to 50 / zm. Is preferred. By appropriately setting the viscosity of the epoxy resin, the curing agent, and the auxiliary polymer or the mixture of Z and auxiliary solvent, the amount of the dispersion stabilizer used, the viscosity of the aqueous dispersion stabilizer solution, the dispersion method and the dispersion conditions within the above range, A droplet average particle size in this range is obtained. The epoxy resin in the droplets and the curing agent are reacted by heating the aqueous solution of the epoxy resin, the curing agent, and the dispersion stabilizer in which the auxiliary polymer or the mixture of Z and the auxiliary solvent is dispersed with stirring. .

[0091] The heating temperature varies depending on the type of epoxy resin and curing agent. Generally, the heating temperature is preferably about 30 to 150 ° C, particularly preferably about 40 to 120 ° C. The time required for the cross-linking reaction varies depending on the type of epoxy resin, curing agent, auxiliary polymer, or Z and auxiliary solvent, but is generally about 3 to 48 hours.

[0092] By performing the crosslinking reaction in this manner, the epoxy resin is cured by crosslinking in the droplets of the epoxy resin, the curing agent, and the auxiliary polymer or the mixture of Z and the auxiliary solvent. In the obtained cured epoxy resin, phase separation is promoted by the presence of the auxiliary polymer and Z or an auxiliary solvent, and as a result, a shell having a single layer structure, that is, a shell made of the cured epoxy resin is formed. On the other hand, the core portion is in a state where an excessive curing agent, an auxiliary polymer and Z or an auxiliary solvent are included.

[0093] The hardener-encapsulated fine particles thus obtained may be recovered from the dispersion by filtration or the like. Also, for example, drying is performed under conditions of a temperature of about 0 to 50 ° C and a pressure of 10 ³ to about L0 ⁵ Pa. Can. It can also be dried by natural evaporation, reduced pressure treatment or the use of a desiccant such as silica gel.

[0094] When the hardener-encapsulated fine particles prepared using an auxiliary solvent are used as a component of a one-component adhesive, the shell may be used in a state where the solvent is enclosed with the hardener in the shell or The solvent may be removed and used forcefully.

(Ii) Hardener phrase, fine particles

The fine particles obtained in this manner are fine particles in which the hollow portion of the hollow fine particles having a shell and a hollow partial force is encapsulated with an epoxy resin hardener, and the shell is substantially encapsulated. Is a fine particle made of a cured epoxy resin obtained by the reaction of the same kind of curing agent and epoxy resin.

[0095] The shell has a single-layer structure made of a cured epoxy resin, and an auxiliary polymer and Z or an auxiliary solvent are enclosed therein together with a curing agent. In some cases, it may have a two-layer structure in which a layer that also has auxiliary polymer strength is formed inside the cured epoxy resin layer, but the amount of auxiliary polymer is significantly less than the amount of cured epoxy resin. Thus, the shell consists essentially of a cured epoxy resin layer.

[0096] The amount of the curing agent encapsulated in the fine particles of the present invention is not particularly limited, but by using the curing agent with respect to the epoxy resin in the above-described ratio, the fine particles of the present invention have 50 to 500 to the shell. The curing agent is contained in an amount of about% by weight, preferably about 100 to 200% by weight.

[0097] The average particle size of the fine particles of the present invention is preferably about 0.1 to 50 µm, more preferably about 0.5 to 20 m. When the average particle size is within the above range, the shell is sufficiently thick to prevent the hardener from leaking and the shell layer can be formed smoothly.

[0098] The average particle size in the present invention is an average value obtained by measuring the particle size of 100 fine particles using an optical microscope.

[0099] In the fine particles of the present invention, the volume ratio R of the encapsulating part of the curing agent is preferably about 10 to 80%, more preferably about 20 to 70%. The volume ratio of the hollow portion is a value represented by the following formula. [0100] R (%) = (rh / rp) ³ X 100

(In the formula, rh is the radius of the hardener encapsulating part of the fine particles, and rp is the radius of the microparticles.) Here, the hardener encapsulating part is the hollow part when the hardener is removed from the microparticles. Say. If the volume ratio of the curing agent-encapsulating portion is in the above range, the thickness of the shell does not become too large, and the shell can be destroyed with an appropriate force when used as a curing agent for a one-component adhesive. In addition, the content of the curing agent is sufficient, and the amount of fine particles can be reduced when preparing a one-component adhesive.

[0101] The volume ratio can be adjusted to the above range by adjusting the mixing ratio of each component in the production method described above, for example. That is, the above volume ratio is calculated by calculating the volume ratio of the curing agent from the usage ratio of the two assuming that the reactivity ratio between the epoxy resin used in the production and the curing agent is 1/1. Can be sought.

[0102] The fine particles of the present invention vary depending on the type of epoxy resin and curing agent, shell thickness, amount of encapsulated curing agent, etc., but when measured using a micro compression tester (manufactured by Shimadzu Corporation). The crushing limit load is usually about 1 to about LOOmN, preferably about 3 to 50 mN. By being in this range, when used as a component of the adhesive composition, it can be easily broken and is not crushed before use in the adhesive composition.

(m) ί liquid type epoxy resin glaze composition

The one-pack type epoxy resin adhesive composition of the present invention comprises the above-described curing agent-containing fine particles of the present invention and epoxy resin.

[0103] The use ratio of the epoxy resin to the fine particles is such that the chemical equivalent ratio of the epoxy resin and the curing agent contained in the composition is epoxy resin: curing agent = 1: 0.5 to 2, preferably Should be used at a ratio of about 1: 1.

[0104] The adhesive composition may contain various additives usually added to the epoxy resin adhesive composition. Different forces depending on the adhesive application Such additives include fillers such as calcium carbonate and magnesium carbonate, flexibility imparting agents such as thermoplastic elastomers, flame retardants such as hydroxyaluminum hydroxide, Reinforcing agents such as glass fiber, conductivity imparting agents such as carbon black, tackifiers such as rosin, dibutyl phthalate Such diluents, thixotropic agents such as finely divided silica, antifoaming agents such as silicone oil, leveling agents such as acrylic resin, release agents such as ester waxes, pigments and the like.

(IV) Bonding method of adherend with epoxy steel

The first adherend adherence method of the present invention includes a step of placing the above-described one-pack type epoxy resin adhesive composition of the present invention between a pair of adherends and pressing the adherends together. More specifically, the method includes a step of releasing the curing agent from the fine particle sheller, and a step of causing the epoxy resin and the curing agent to undergo a crosslinking reaction to bond the adherends. As a result, cross-linked epoxy resin is generated and the adherends are adhered to each other.

Also, instead of placing the one-component epoxy resin adhesive composition between a pair of adherends, the curing agent-encapsulated fine particles and the epoxy resin described above are mixed between the pair of adherends. You can also.

Here, “placement” is a concept that includes spotting in addition to application.

[0106] The reaction between the epoxy resin and the curing agent is preferably performed at about 30 to 150 ° C, more preferably about 40 to 120 ° C!

(V) Isoshiane Tsunazuna> Phrase, notice of fine particles ^

The production method of the present invention is a method for producing fine particles in which an active hydrogen compound or polyisocyanate selected from the group consisting of polyol, polyamine, and polythiol force is encapsulated in a hollow portion of a hollow fine particle having a shell and a hollow partial force. is there. This method comprises a first step of dispersing a mixture containing a polyisocyanate and the active hydrogen compound in an aqueous dispersion stabilizer solution; a polyaddition reaction of the polyisocyanate and the active hydrogen compound. 2 processes. This mixture contains the active hydrogen compound at a chemical equivalent ratio of about 2 to 25 with respect to the polyisocyanate, or a chemical equivalent ratio of about 2 to 25 with respect to the active hydrogen compound. Contains polyisocyanate in proportions.

Dispersion stabilizer

A wide range of dispersion stabilizers have the effect of preventing droplets formed by dispersing a mixture of a polyisocyanate, an active hydrogen compound, and an auxiliary polymer or auxiliary solvent in water to coalesce. Power available. [0107] For example, polybulol alcohol, methylcellulose, ethylcellulose, polyacrylic acid, polyacrylimide, polyethyleneoxide, poly (nodoxystearic acid g-methyl methacrylate-co-methacrylic acid) copolymer, etc. Examples thereof include molecular dispersion stabilizers, non-ionic surfactants, anionic surfactants, and amphoteric surfactants. Among these, polymer dispersion stabilizers such as polyvinyl alcohol are preferable.

[0108] The amount of the dispersion stabilizer used can be selected from a wide range. Generally, 0.001 to 1 part by weight with respect to 1 part by weight of the mixture of polyisocyanate, active hydrogen compound, and auxiliary polymer or auxiliary solvent. It is preferable that the amount is about 0.01 to 0.5 parts by weight.

[0109] Further, in the dispersion stabilizer aqueous solution, the concentration of the dispersion stabilizer may be appropriately selected so that the droplets do not coalesce. Generally, it is preferable to adjust the concentration of the aqueous dispersion stabilizer solution to a range of about 0.05 to 5% by weight, particularly about 0.1 to 2% by weight.

Polyisocyanate

The polyisocyanate is preferably poorly water soluble, but this requirement is usually met.

[0110] The polyisocyanate is not particularly limited, and a known compound having two or more isocyanate groups in one molecule can be used. For example, 4,4'-diphenylmethane diisocyanate (MDI), hydrogenated carbonate MDI, 4,4,1-biphenyl diisocyanate tridene diisocyanate, isophorone diisocyanate, 1 , 3 xylylene diisocyanate, 1,4-xylene diisocyanate, p-tetramethylxylene diisocyanate, m-tetramethylxylene diisocyanate, 2,4 tolylene diisocyanate, 2,6 tolylene diisocyanate, 1,5 naphthalene diisocyanate, m-phenolic diisocyanate, p-phenolic diisocyanate, triphenol-dimethane triisocyanate, 4,4'-dicyclohexylenomethane diisocyanate, 1,4-tetramethylene Diisocyanate, 1, 6 Hexamethylene diisocyanate, 1, 8 Ottamethylene diisocyanate, L-Lysine diisocyanate 1, 6, 11 —Undecane triisocyanate, 4, 4 ', 4 "—Triphenylmethane triisocyanate, 2, 4, 4, 1-biphenyl triisocyanate, 2, 4 4, 4-diphenylmethane triisocyanate, polymethylenephenol isocyanate, etc. Polyisocyanate alone or Can be used in combination of two or more.

[0111] In particular, isophorone diisocyanate is preferred as such polyisocyanate, which is preferably liquid at room temperature in terms of good workability in the first step of dispersing droplets containing polyisocyanate. , Diphenylmethane diisocyanate, methylene diisocyanate, Coronate HX manufactured by Nippon Polyuretan Kogyo Co., Ltd.

Can be mentioned. Of these, isophorone diisocyanate is more preferable.

[0112] Further, the ability to use both a bifunctional isocyanate and a trifunctional isocyanate. A trifunctional isocyanate is more preferred in that the shell made of isocyanate resin has a strength capable of holding the inclusion component for a long period of time.

7k chemicals

In the present invention, as the active hydrogen compound, a compound selected from the group consisting of polyol, polyamine, and polythiolca is used. Polyols react with polyisocyanates to give polyurethane resins, polyamines react with polyisocyanates to give polyurea resins, and polythiols react with polyisocyanates to give polythiourethane resins.

[0113] The active hydrogen compounds may be used alone or in combination of two or more. For example, a polyol and a polyamine can be mixed and used.

As the polyol, known oil-soluble polyalcohol can be widely used as a raw material for producing polyurethane. Specifically, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, tetramethylene glycol (1,3- or 1,4-butylene glycol), tetramethylene ether glycol, neopentyl glycol, 1,6-hexamethylene glycol, decamethylene glycol, nonanediol, dodecanediol, bisphenol A, bisphenol F, p-xylylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, etc. Is mentioned.

[0114] Further, a polymer or copolymer of these low molecular weight polyalcohols, or one or more of these low molecular weight alcohols may be ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide, or the like. Add seeds or more than two And polyether polyalcohol obtained by the above.

[0115] Further, one or more of these low molecular weight polyalcohols or their alkylene oxide adducts, and malonic acid, maleic acid, succinic acid, adipic acid, glutaric acid, pimelic acid, sebacic acid Polyester polyalcohol obtained by reacting one or more of oxalic acid, oxalic acid, phthalic acid, isophthalic acid, terephthalic acid, hexahydrophthalic acid, etc .; ring opening of cyclic esters such as propiolataton, butyrolataton, and force prolataton Examples include polyester polyalcohol obtained by polymerization; polyester polyalcohol obtained from polyalcohol and cyclic ester, and the like.

[0116] As the polyether polyalcohol or polyester polyalcohol, those having a molecular weight of about 80 to 300, particularly about 100 to 200 can be used.

[0117] In particular, polyester alcohol is more preferable among polyether polyalcohol and polyester polyalcohol because they are poorly water-soluble and easy to disperse in water.

The type of polyamine is not particularly limited, and polyamines usually used for polyurea production can be used without limitation.

[0118] Examples of such polyamines include ethylenediamine, isophoronediamine, 3,9panamine-

2, 4, 8, 10—Tetra-xiaspirodoundecane, lysine, phenylenediamine, 2, 2, 4 trimethylhexamethylenediamine, tolylenediamine, hydrazine, piperazine, hexamethylenediamine, propylenediamine , Dicyclohexylmethane 4,4-diamin, 2 hydro

—Diamines such as hydroxypropylethylenediamine and modified aliphatic amine can be mentioned.

[0119] Among them, the solubility in water is low and the viscosity is low, so that it can be easily dispersed in water.

3,9Panamine-2,4,8,10-Tetraoxaspirodoundecane and modified aliphatic amines are preferred, and modified aliphatic amines are more preferred.

<Po> 2 Chionore> For example, 1,2-ethanedithiole, 1,2-propanedithiol, 1,3 propanedithiol, 1,4 butanedithiol, 1,5 pentanedithiol, 1,6 hexanedithiol, 1,7 heptanedithiol, 1,8 octanedithiol, 1,9-nonanedithiol, 1,10 decanedithiol, 1,12 dodecanedithiol, 2,2 dimethyl-1,3 propanedithiol, 3-methyl-1,5-pentanedithiol, 2-Methyl-1,8 octanedithiol, 1,4-cyclohexanedithiol, 1,4 bis (mercaptomethyl) cyclohexane, 2 mercaptoethyl ethercaptomethyl) 1,4 dioxane, 2,5 bis (mercaptomethyl) 1 , 4-dithiane, 1, 1, 1-tris (mercaptomethyl) ethane, 2-ethylol 2-mercaptomethyl-1, 3- Pandithiol, tetrakis (mercaptomethyl) methane, 3,3'-thiobis (propane 1,2 dithiol), 2,2, -thiobis (propane 1,3 dithiol), pentaerythritol tetrakis (mercaptopropionate), pentaerythritol Aliphatic polythiols such as tetrakis (mercaptoacetate);

1,2 benzenedithiole, 1,3 benzenedithiole, 1,4 benzenedithiol, 1,3,5 benzenetrithiol, 1,2 bis (mercaptomethyl) benzene, 1,3 bis (mercaptomethyl) benzene, Aromatic polythiols such as 1,4 bis (mercaptomethyl) benzene, 1,3,5 tris (mercaptomethyl) benzene, toluene 3,4-dithiol.

In particular, 1,1 2-dodecanedithiol is preferred, and 1,12-dodecanedithiol is preferred.

Combination of polyisocyanate and active hydrogen compound

Preferred combinations of polyisocyanates and active hydrogen compounds include combinations of isophorone diisocyanate and modified aliphatic amines, combinations of isophorone diisocyanate and dodecane diol, methylene diisocyanate (eg Millionate MR —200 (trade name)) with a modified aliphatic amine, Coronate HX (trade name) with a modified aliphatic amine, isophorone diisocyanate and 3,9panamamine-2, 4, 8, 10 —Combination with tetraoxaspirodoundecane. [0121] When the active hydrogen compound is excessive, the chemical equivalent ratio of the polyisocyanate to the active hydrogen compound is polyisocyanate: active hydrogen compound = about 1 to 2 to 25, preferably 3 to 23 The degree may be adjusted to about 4 to 20, more preferably. The chemical equivalent ratio here is the ratio of the number of isocyanate groups of the polyisocyanate to the number of active hydrogen donor groups of the active hydrogen compound. That is, in this case, if the amount of the active hydrogen compound is determined so that the number of active hydrogen donating functional groups of the active hydrogen compound is about 2 to 25 with respect to the number of isocyanate groups of the polyisocyanate, Good.

[0122] By using an excess amount of the active hydrogen compound relative to the polyisocyanate in this way, an excess of the active hydrogen compound that does not participate in shell formation is taken into the hollow portion in the shell. In addition, if the amount of active hydrogen compound used relative to polyisocyanate is too large, it is difficult to produce isocyanate resin, but if it is within the above range, shell formation is caused by polyaddition reaction of polyisocyanate and active hydrogen compound Is done quickly.

[0123] On the other hand, when polyisocyanate is used in excess, the chemical equivalent ratio of active hydrogen compound and polyisocyanate active hydrogen compound: polyisocyanate = 1: 2 to 25, preferably It may be about 3 to 23, more preferably about 4 to 20. In this case, the amount of polyisocyanate used may be determined so that the number of isocyanate groups in the polyisocyanate is about 2 to 25 with respect to the number of active hydrogen donor groups in the active hydrogen compound.

[0124] By using an excess amount of polyisocyanate relative to the active hydrogen compound in this way, excess polyisocyanate not involved in shell formation is taken into the hollow portion of the shell. In addition, if the amount of polyisocyanate used in the active hydrogen compound is too large, it is difficult to produce isocyanate resin, but if it is within the above range, shell formation by polyaddition reaction of polyisocyanate and active hydrogen compound may occur. Done quickly.

Auxiliary polymer

The mixture dispersed in the aqueous solution of the dispersion stabilizer preferably contains the following auxiliary polymer or auxiliary solvent in addition to the polyisocyanate and the active hydrogen compound.

[0125] That is, the compatibility between the isocyanate obtained by the reaction of the polyisocyanate and the active hydrogen compound is low, and the interfacial tension between the auxiliary polymer or auxiliary solvent and water (γ (mN / m) and the interfacial tension (γ ^y ) (mN / m) between isocyanate resin and water Incidentally, it is an auxiliary polymer or auxiliary solvent that satisfies the condition of γ ^χ ≥ γ ^y (condition A).

[0126] The polymer or solvent should be low and compatible with the isocyanate resin obtained by the polyaddition reaction between polyurethane and an active hydrogen compound (Condition B).

[0127] Specifically, as the auxiliary polymer and the auxiliary solvent, those having a lower polarity than the isocyanate resin obtained by polyaddition reaction between polyurethane and an active hydrogen compound can be used.

[0128] In the present specification, the compatibility of the auxiliary polymer and the auxiliary solvent with isocyanate is measured by the following method. That is, an active hydrogen compound (equivalent chemical equivalent to polyisocyanate) is added to a solution containing polyisocyanate, which is a raw material of isocyanate, an auxiliary polymer or auxiliary solvent, and if necessary, toluene in an appropriate weight ratio. ) Is added to cause a polyaddition reaction in a nitrogen gas atmosphere at 70 ° C. This reaction is carried out in a quartz glass cell having an optical path length of 1 cm, and the light transmittance is measured over time when irradiated with light having a wavelength of 550 nm. As the concentration of the auxiliary polymer or auxiliary solvent is increased, the permeability, which was initially about 100%, rapidly decreases to near 0% as the crosslinking time elapses due to phase separation of the isocyanate chain. In this case, if the compatibility between the auxiliary polymer or auxiliary solvent and the isocyanate resin is low, it decreases to nearly 0%. However, if the compatibility between the auxiliary polymer or auxiliary solvent and the isocyanate resin is high, the transmittance is almost reduced. do not do. In addition, the lower the compatibility between the auxiliary polymer or auxiliary solvent and the isocyanate resin, the shorter the time from the start of curing until the decrease in transmittance occurs.

[0129] As an auxiliary polymer or auxiliary solvent having low compatibility with isocyanate resin, when the transmittance is measured by the above method, the crosslinking ratio of polyisocyanate is about 20% to about 20%, preferably Auxiliary polymers or cosolvents that cause a decrease in transmittance at about 1 to 10%.

[0130] Further, in the present invention, the interfacial tension is a value measured by the Duny platinum ring method defined in ASTM-971-50.

[0131] The auxiliary polymer and the auxiliary solvent are desirably soluble in a mixture of polyisocyanate and active hydrogen compound, but this requirement is usually satisfied.

[0132] The auxiliary polymer and the auxiliary solvent satisfying the conditions A and B are polyisocyanate and And promotes phase separation between the active hydrogen compounds and isocyanate resin obtained by their polyaddition reaction. Furthermore, in a mixture of polyisocyanate, active hydrogen compound, auxiliary polymer or Z and auxiliary solvent, the polyisocyanate reacts with the active hydrogen compound to form an isocyanate resin, which is then mixed with water. When adsorbed on the interface, the isocyanate resin is more easily adsorbed on the interface with water than the auxiliary polymer or Z and auxiliary solvent. As a result, fine particles having a shell made of isocyanate resin are obtained. It is done. At this time, as described above, since the isocyanate or the active hydrogen compound is excessively present, the excess component is taken into the shell together with the auxiliary polymer or Z and the auxiliary solvent.

[0133] As the auxiliary polymer, for example, polystyrene, polymethyl methacrylate, polybutyl methacrylate and the like can be used. In addition, the auxiliary polymer preferably has a molecular weight of about 100,000 to 300,000, and in this range, the phase separation is sufficiently promoted and a mixture containing a polyisocyanate, an active hydrogen compound, and an auxiliary polymer or auxiliary solvent. Viscosity does not increase so much. One auxiliary polymer can be used alone, or two or more auxiliary polymers can be used in combination.

[0134] The combination of the polyisocyanate, the active hydrogen compound and the auxiliary polymer that satisfies the conditions A and B is a force that can be easily selected by the above-described method, for example, isophorone diisocyanate. And a combination of a modified aliphatic amine and polymethyl methacrylate.

[0135] As the auxiliary solvent, a solvent having about 12 to 16 carbon atoms that is liquid at room temperature can be used. Such solvents include linear and branched aliphatic hydrocarbon solvents such as dodecane, tridecane, tetradecane, pentadecane, hexadecane; cyclohexyl benzene, 1,2-dimethylnaphthalene, 1,3-dimethyl Aromatic hydrocarbon solvents such as naphthalene and 1,6-dimethylnaphthalene; ether solvents such as dibenzyl ether; triethyl acetyltaenoate, isoamyl benzoate, benzyl benzoate, isoamyl salicylate, benzyl salicylate, sulphur Examples include ester solvents such as diamyl acid, dibutyl tartrate, and jetyl phthalate; nitrogen-containing solvents such as dioctylamine, dicyclohexylamine, Ν, Ν-dibutylamine, triamylamine, and tri-η-ptyramine. Co-solvents can be used alone or in combination of two or more.

[0136] Polyisocyanate, active hydrogen compound and auxiliary solution satisfying conditions Α and Β The combination with the medium can be easily selected by the above-described method, for example, a combination of isophorone diisocyanate, modified aliphatic amine and hexadecane.

[0137] When the polyisocyanate and the active hydrogen compound themselves satisfy the conditions A and B, respectively, the auxiliary polymer or the auxiliary solvent may not necessarily be used. In this case, the polyisocyanate and the active hydrogen compound function as a phase separation agent to promote shell formation.

[0138] The amount of the auxiliary polymer used is not limited to this, but is about 0.01 to 2 parts by weight with respect to 1 part by weight of the total amount of polyisocyanate and active hydrogen compound.

In particular, the content is preferably about 0.02-0. 1 part by weight.

[0139] The amount of co-solvent used is not limited to this, but it is about 0.1 to 5 parts by weight, especially about 0.1 to 1 part by weight of the total amount of polyisocyanate and active hydrogen compound. The amount is preferably about 5 to 2 parts by weight.

[0140] If the amount of the auxiliary polymer and Z or auxiliary solvent used is in the above range, the shell is sufficiently formed, and the amount of the isocyanate resin component is relatively small. In the present invention, a suspension containing a polyisocyanate, an active hydrogen compound, an auxiliary polymer or a mixture containing Z and an auxiliary solvent in the above-mentioned proportions is dispersed in an aqueous dispersion stabilizer solution, and a suspension crosslinking reaction is performed.

[0141] In the dispersion step, the active hydrogen compound and the auxiliary polymer or Z and the auxiliary solvent are preferably dissolved in the polyisocyanate to form a uniform solution. The temperature at the time of mixing is not particularly limited. For example, it may be about 0 to 30 ° C.

[0142] The polyisocyanate thus obtained, the active hydrogen compound, and the auxiliary polymer or the mixture of Z and the auxiliary solvent are dispersed in an aqueous solution of a dispersion stabilizer.

[0143] The homogeneous solution is preferably used in an amount of about 1 to 200 parts by weight, particularly about 5 to about LOO parts by weight, per 100 parts by weight of the aqueous dispersion stabilizer solution. It is not limited. [0144] The dispersion method is not particularly limited, and a known method may be employed. Examples of such known dispersion methods include a method using a homogenizer and a dispersion method using mechanical shearing force such as a membrane emulsification method. The temperature condition during dispersion is not limited to this, but it may be about 0 to 30 ° C.

[0145] In the dispersion method exemplified above, the size of droplets formed by dispersing a polyisocyanate, an active hydrogen compound, and an auxiliary polymer or a mixture of Z and an auxiliary solvent is not limited to a single dispersion. The droplets having different particle sizes are mixed. Therefore, the fine particles finally obtained also have different particle sizes.

[0146] On the other hand, by selecting a dispersion method, it is possible to make the size of the droplets uniform and obtain monodispersed droplets. As a method for obtaining such monodispersed droplets, for example, a method of producing monodispersed droplets by a membrane emulsification method using porous glass (SPG) or a seed swelling method (see JP-A-8-20604). And the like).

[0147] When such monodispersed droplets having a uniform particle size are prepared, the finally obtained isocyanate resin component-containing fine particles are also monodispersed with a uniform particle size. The monodispersed isocyanate-containing resin-encapsulated fine particles have uniform fracture conditions when used as a one-component epoxy resin adhesive. As a result, an adhesive with a uniform concentration distribution of the encapsulated component and thus a uniform adhesive force is obtained. can get.

[0148] Even in the case of V deviation, the average particle size of the droplets may be determined as appropriate according to the desired average particle size of the isocyanate-containing component-containing fine particles, but is generally 0.1 to 50. It is preferably about m. Viscosity of polyisocyanate, active hydrogen compound, auxiliary polymer or mixture of Z and auxiliary solvent, amount of dispersion stabilizer used, viscosity of aqueous dispersion stabilizer solution, dispersion method 'dispersion conditions' are appropriately set within the above range. Thus, an average particle diameter in this range can be obtained. By heating an aqueous solution of a polyisocyanate, an active hydrogen compound, and an auxiliary polymer or a dispersion stabilizer in which a mixture of z and an auxiliary solvent is dispersed with stirring, the polyisocyanate and the active hydrogen compound in the droplets are heated. And react.

[0149] The reaction temperature varies depending on the type of polyisocyanate and active hydrogen compound. In general, about 20 to 150 ° C, particularly about 30 to 120 ° C is preferable. The time required for the polyaddition reaction is generally about 3 to 48 hours depending on the type of polyisocyanate, active hydrogen compound, auxiliary polymer or Z and auxiliary solvent.

[0150] By setting the temperature of the reaction system within the above range, the polyisocyanate, the active hydrogen compound, and the auxiliary polymer or the mixture of Z and the auxiliary solvent are mixed with each other. A polyaddition reaction produces isocyanate resin and cures. In the obtained isocyanate resin, phase separation is promoted by the presence of the auxiliary polymer and Z or auxiliary solvent, and as a result, a shell having a single layer structure, that is, a shell made of isocyanate resin is formed. On the other hand, the core portion is in a state where an excess polyisocyanate or active hydrogen compound, an auxiliary polymer and Z or an auxiliary solvent are encapsulated.

[0151] The isocyanate-containing resin-encapsulated fine particles thus obtained may be recovered from the dispersion by filtration or the like. For example, it can be dried under conditions of a temperature of about 0 to 50 ° C. and a pressure of about 10 ³ to about L0 ⁵ Pa. It can also be dried by natural evaporation, reduced pressure treatment, or using a desiccant such as silica gel.

[0152] When using isocyanate-containing resin-encapsulated microparticles prepared using an auxiliary solvent as a component of a one-pack type adhesive, use it with the solvent encapsulated in the shell together with the isocyanate-containing resin component. Alternatively, the force may be used by removing the solvent.

Isocyanane rosin component internal phrases, fine particles

The fine particles obtained in this way are fine particles in which an active hydrogen compound or polyisocyanate selected from the group consisting of polyol, polyamine, and polythiol force is encapsulated in the hollow portion of the hollow fine particles also having a shell and a hollow partial force. In this case, the shell force is a fine particle substantially consisting of an isocyanate resin obtained by a polyaddition reaction of the same kind of component as the encapsulated component with a polyisocyanate or the above active hydrogen compound.

[0153] The shell has a single-layer structure made of isocyanate resin, in which an auxiliary polymer and Z or an auxiliary solvent are enclosed together with a polyisocyanate or an active hydrogen compound.

[0154] The isocyanate resin constituting the shell is a polyurethane resin when a polyol is used as the active hydrogen compound, and a polyol is used when a polyamine is used as the active hydrogen compound. Liurea resin, and polythiourean resin when polythiol is used as the active hydrogen compound. For example, when a polyol and a polyamine are used, a shell made of an isocyanate resin containing both a urethane bond and a urea bond is formed. In this case, if one of the active hydrogen compounds is extremely reactive with the polyisocyanate, it is highly reactive! If the component forms a shell and is less reactive, the component is encapsulated in the shell.

[0155] In some cases, it may have a two-layer structure in which an auxiliary polymer force layer is formed inside the isocyanate resin layer, but the amount of auxiliary polymer is significantly higher than the amount of isocyanate resin. Less so, the shell consists essentially of the isocyanate resin layer.

[0156] The amount of the isocyanate component in the fine particles of the present invention, that is, the excess component of the polyisocyanate or the active hydrogen compound is not particularly limited, but the polyisocyanate and the polyisocyanate have the above-mentioned ratio. the use of the active hydrogen compound, fine particles of the present invention, 50 to 1500% approximately relative to the shell, preferably the ones containing the 100-1000 weight ^_0/0 approximately Isoshi Aneto榭脂components.

[0157] The average particle size of the fine particles of the present invention is preferably about 0.1 to 50 µm, more preferably about 0.5 to 20 m. When the average particle size is within the above range, the shell is sufficiently thick and the enclosed components are difficult to leak, and the shell layer can be formed smoothly.

[0158] The average particle diameter in the present invention is an average value obtained by measuring the particle diameters of 100 fine particles using an optical microscope.

[0159] In the fine particles of the present invention, the volume ratio R of the encapsulated portion (hollow portion) of the isocyanate resin component is preferably about 30 to 95%, more preferably about 50 to 90%. Yes. The volume ratio R of the hollow portion is a value represented by the following formula.

[0160] R (%) = (rh / rp) ³ X 100

(In the formula, rh is the radius of the isocyanate resin component-containing part of the fine particles, and rp is the radius of the fine particles.)

Here, the isocyanate-containing component-containing portion means a hollow portion when the fine particle force is removed from the isocyanate-containing component. If the volume ratio of the isocyanate resin component inclusions is in the above range, the shell will not be too thick. When used as a component, the shell can be broken with an appropriate force. Also

Therefore, the content of isocyanate component is sufficient, and the amount of fine particles can be reduced when preparing a one-component adhesive.

[0161] The volume ratio can be adjusted to the above range by adjusting the mixing ratio of each component in the production method described above, for example. That is, the above volume ratio is calculated by calculating the volume ratio of the inclusion component from the usage ratio of the polyisocyanate used in the production, assuming that the reactivity ratio of the active hydrogen compound is 1/1. Can also be determined.

[0162] The fine particles of the present invention vary depending on the types of polyisocyanate and active hydrogen compound, shell thickness, amount of inclusion of isocyanate resin components, etc., but a micro compression tester (manufactured by Shimadzu Corporation) is used. The crushing limit load is usually about 1 to 100 mN, preferably about 3 to 50 mN. By being in this range, when used as a component of the adhesive composition, it can be easily broken and is not crushed before use in the adhesive composition.

(V) ί liquid type isocyanate binder composition

The one-component isocyanate resin adhesive composition of the present invention can form a isocyanate resin by polyaddition reaction with the above-described fine particles encapsulating the isocyanate composition of the present invention and the components encapsulated in the fine particles. And a counter component. That is, when the polyisocyanate is encapsulated in the fine particles, the composition contains the fine particles and the active hydrogen compound. When the active hydrogen compound is encapsulated in the fine particles, the composition contains the fine particles and the polyisocyanate. It is a thing.

[0163] The use ratio of the fine particles to the component is determined by the chemical equivalent ratio of all polyisocyanates and all active hydrogen compounds contained in the composition. Polyisocyanate: active hydrogen compounds = 1: 0.5 The ratio should be about ˜2, preferably about 1: 1.

[0164] The adhesive composition may also contain various additives that are usually added to isocyanate isocyanate resin compositions. Depending on the application of the adhesive, such additives include fillers such as calcium carbonate and magnesium carbonate, flexibility imparting agents such as thermoplastic elastomers, and flame retardants such as hydroxyaluminum hydroxide. Reinforcing agent such as glass fiber, conductivity imparting agent such as Bonbon Black, tackifier imparting agent such as rosin, dibuty phthalate Diluting agents such as silica, thixotropic agents such as finely divided silica, antifoaming agents such as silicone oil, leveling agents such as acrylic resin, release agents such as ester wax, pigments, etc. I can get lost.

[0165] This composition was applied between a pair of adherends, and by pressing them, the shell of fine particles was broken and the encapsulated polyisocyanate or active hydrogen compound was released, and the composition was Reacts with isocyanate resin.

(VI) Bonding method of adherends with isocyanate steel

The second adherend adhesion method of the present invention includes the step of placing the above-described one-component isocyanate resin adhesive composition of the present invention between a pair of adherends and pressing the adherends together. The method includes a step of releasing an isocyanate resin component from the fine particle shell, and a step of adhering the adherend by polyaddition reaction of the isocyanate resin component and its counter component. Thereby, isocyanate resin is produced | generated and adherends adhere.

[0166] Further, instead of placing the one-component isocyanate resin-adhesive composition between a pair of adherends, the above-described isocyanate resin component-encapsulating fine particles and the counter-component are placed between a pair of adherends. Can also be mixed.

[0168] The reaction between the polyisocyanate and the active hydrogen compound is preferably performed at about 20 to 150 ° C, more preferably about 30 to 120 ° C! /.

Leakage

The first use of the present invention is a fine particle in which a hollow portion of a hollow fine particle having a shell and a hollow partial force is encapsulated with a hardener of epoxy resin, and the shell force is substantially equal to the encapsulated hardener and This is the use of a hardener-encapsulated fine particle, which consists of a hardened epoxy resin obtained by reaction of the same kind of hardener and epoxy resin, as a hardener for a one-pack type epoxy resin adhesive.

[0169] In the second use of the present invention, an active hydrogen compound or polyisocyanate selected from the group consisting of a polyol, a polyamine, and a polythiol force is encapsulated in the hollow part of the hollow fine particle having a shell and a hollow partial force. It is a fine particle and has a shell force substantially in the polyaddition reaction of the same type of component as the encapsulated component with the polyisocyanate or the active hydrogen compound. This is the use of isocyanate resin component-encapsulated fine particles comprising the isocyanate resin obtained as a one-component isocyanate resin adhesive component.

Example

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.

Measurement was performed using a micro compression tester (manufactured by Shimadzu Corporation).

Measurement was performed on 100 fine particles using an optical microscope, and an average value was obtained.

Assuming that the reactivity ratio between the epoxy resin used in the production and the curing agent is 1/1, the volume ratio of the curing agent was calculated from the usage ratio of both. This ratio was regarded as the volume ratio of the hollow part of the fine particles when the curing agent was excluded.

<Isocyanate> Phrase> Assuming that the reactivity ratio between the polyisocyanate used in the production and the active hydrogen compound is 1/1, the volume ratio of the encapsulated components was also calculated. This ratio was regarded as the volume ratio of the hollow part of the fine particles when the inclusion component was excluded.

m Epoxy spirit hardening agent phrases, examples of observation of fine particles

Example 1 1

10 g of an aqueous solution obtained by dissolving 150 mg of polybulal alcohol as a dispersion stabilizer (A) in water, 189 mg of bisphenol F-type glycidyl ether (manufactured by Japan Epoxy Resin, Epicoat 806) as an epoxy resin (B), tetraglycidyl diamine Minophenylmethane (Japan Epoxy Resin, Epicoat 604) 132mg, 3,9 Panam-2, 4,8,10-Tetraoxaspiro [5,5] undecane (Japan Epoxy Resin) as hardener (C) , Epicure RX-3) 930 mg, and an auxiliary polymer (D) 34 mg of polymethyl methacrylate as a uniform mixture were suspended.

[0170] The chemical equivalent ratio of epoxy resin to curing agent is epoxy resin: curing agent = 1: 5.

[0171] The suspension method uses a homogenizer as an apparatus, a stirring speed of 1000 rpm, and a condition at room temperature. I went under the matter. The resulting suspension droplets had an average particle size of about 10 m.

[0172] Next, the suspension was heated at 30 ° C and subjected to polyaddition reaction for 4 hours.

When the obtained dispersion was observed with an optical microscope, a uniform structure was observed, and the shell layer was observed by dispersing in tetrahydrofuran and extracting the curing agent, resulting in a hardener capsule and polymer fine particles. .

[0173] The obtained fine particles had an average particle diameter of 10 µm, and the volume ratio of the curing agent-encapsulating portion was 50%. The amount of hardener contained in the shell was 50% by weight. The crushing limit load was 10 mN.

10 g of an aqueous solution obtained by dissolving 150 mg of polybulal alcohol as a dispersion stabilizer (A) in water, 378 mg of bisphenol F-type glycidyl ether (manufactured by Japan Epoxy Resin, Epicoat 806) as an epoxy resin (B), a curing agent (C ) 3,9 Panam-2,4,8,10-tetraoxaspiro [5,5] undecane (Japan Epoxy Resin, Epicure RX-3) 9 30 mg, polymethyl methacrylate 34 mg as auxiliary polymer (D) A uniformly mixed solution was suspended.

[0174] The chemical equivalent ratio between the epoxy resin and the curing agent is epoxy resin: curing agent = 1: 5.

[0175] The suspension method was carried out using a homogenizer as an apparatus and stirring conditions of 1000 rpm and room temperature. The resulting suspension droplets had an average particle size of about 10 m.

[0176] Next, the suspension was heated at 30 ° C and subjected to polyaddition reaction for 4 hours.

When the obtained dispersion was observed under a microscope, a uniform structure was observed. By dispersing in tetrahydrofuran and extracting the curing agent, a shell layer was observed, and polymer particles encapsulated in the curing agent were obtained.

[0177] The obtained fine particles had an average particle size of 10 µm and a volume ratio of the curing agent-encapsulating portion was 50%. The amount of hardener contained in the shell was 50% by weight. The crushing limit load was 3 mN.

Comparative example 1 1 When no auxiliary polymer is used

10 g of an aqueous solution obtained by dissolving 150 mg of polybulal alcohol as a dispersion stabilizer (A) in water, 189 mg of bisphenol F-type glycidyl ether (manufactured by Japan Epoxy Resin, Epicoat 806) as an epoxy resin (B), tetraglycidyl diamine Minophenylmethane (Japan Epoxy Resin, Epicoat 604) 132mg, 3,9 Panam-2, 4,8,10-Tetraoxaspiro [5,5] undecane (Japan Epoxy Resin) as hardener (C) , Epicure RX-3) 930 mg of an auxiliary polymer-free system formed by homogeneous mixing was suspended.

[0178] The chemical equivalent ratio of epoxy resin to curing agent is epoxy resin: curing agent = 1: 5.

[0179] The suspension was carried out using a homogenizer as an apparatus and stirring conditions of 1000 rpm and room temperature. The obtained suspension droplets had an average particle size of about 10 m.

[0180] Next, the suspension was heated at 30 ° C and subjected to polyaddition reaction for 4 hours.

When the obtained dispersion was observed with a microscope, a uniform structure was observed. When dispersed in tetrahydrofuran, the entire particles were dissolved. When there is too little curing agent by sticking to the epoxy rope

10 g of an aqueous solution obtained by dissolving 150 mg of polybulal alcohol as a dispersion stabilizer (A) in water, 189 mg of bisphenol F-type glycidyl ether (manufactured by Japan Epoxy Resin, Epicoat 806) as an epoxy resin (B), tetraglycidyl diamine Minophenylmethane (Japan Epoxy Resin, Epicoat 604) 132mg, 3,9 Panam-2, 4,8,10-Tetraoxaspiro [5,5] undecane (Japan Epoxy Resin) as hardener (C) , Epicure RX-3) 186 mg and polymethyl methacrylate 34 mg as auxiliary polymer (D) were uniformly mixed.

[0181] The chemical equivalent ratio between the epoxy resin and the curing agent is epoxy resin: curing agent = 1: 1.

[0182] The suspension was carried out using a homogenizer as an apparatus and stirring conditions of 1000 rpm and room temperature. The resulting suspension droplets had an average particle size of about 10 m.

[0183] Next, the suspension was heated at 30 ° C and subjected to polyaddition reaction for 4 hours. When the obtained dispersion was observed with a microscope, a uniform structure was observed. It is thought that there was no hardener to encapsulate because there was too little hardener.

Comparative example 1 3

If there is too much curing agent on the epoxy resin

10 g of an aqueous solution obtained by dissolving 150 mg of polybulal alcohol as a dispersion stabilizer (A) in water, 189 mg of bisphenol F-type glycidyl ether (manufactured by Japan Epoxy Resin, Epicoat 806) as an epoxy resin (B), tetraglycidyl diamine Minophenylmethane (Japan Epoxy Resin, Epicoat 604) 132mg, 3,9 Panam-2, 4,8,10-Tetraoxaspiro [5,5] undecane (Japan Epoxy Resin) as hardener (C) , Epicure RX-3) 3500 mg, and a solution prepared by uniformly mixing 34 mg of polymethyl methacrylate as auxiliary polymer (D) was suspended.

[0184] The chemical equivalent ratio of epoxy resin to curing agent is epoxy resin: curing agent = 1:19.

[0185] The suspension was carried out using a homogenizer as an apparatus, under the conditions of stirring speed of 1000 rpm and room temperature. The resulting suspension droplets had an average particle size of about 10 m.

[0186] Next, the suspension was heated at 30 ° C and subjected to polyaddition reaction for 4 hours.

When the obtained dispersion was observed with a microscope, a uniform structure was observed. When the dispersion was dispersed in tetrahydrofuran, the entire particles were dissolved, and no hardener-encapsulated polymer fine particles were obtained.

Formulation example of 1-pack type epoxy resin adhesive composition

The chemical equivalent ratio of the curing agent capsule polymer fine particles obtained in Example 1 and epoxy resin bisphenol F-type glycidyl ether (manufactured by Japan Epoxy Resin, Epicoat 806) is 1: 1 (capsule resin curing agent: epoxy resin) It mixed so that it might become a one-pack type adhesive agent.

[0187] 10mm X 50mm X 1mm using an aluminum plate two, one-part adhesive as the adhesive area lcm ² is applied, the two aluminum plates were pressed in a vice.

[0188] A tensile shear test was performed using an autograph (manufactured by Shimadzu Corporation) for one day at room temperature or 70 ° C. Those left at room temperature did not show adhesiveness, but those left at 70 ° C were firmly bonded and showed an adhesive strength of about 200 NZcm ² . Fine particles It is considered that the curing agent and epoxy resin released by the destruction of the child were crosslinked by heating.

From this, it can be seen that the epoxy resin composition containing the curing agent-encapsulating fine particles of the present invention can be practically used as a one-component adhesive.

(II) Example of manufacturing fine particles containing isocyanate components

Example 2-1 (when polyisocyanate is vortex II)

30 g of an aqueous solution obtained by dissolving 300 mg of polyvinyl alcohol as a dispersion stabilizer in water, and isophorone diisocyanate as a polyisocyanate (Wako Pure Chemical Industries, Ltd.,

094-03025) 1709 mg, modified aliphatic polyamine as active hydrogen compound (Japan Epoxy Resin Co., Ltd., YLH1204 244 mg, polymethyl methacrylate as an auxiliary polymer (molecular weight: 120,000) 8.5 mg I let you.

[0190] The chemical equivalent ratio of the polyisocyanate to the active hydrogen compound is polyisocyanate: active hydrogen compound = 5: 1.

[0191] The suspension was carried out using a homogenizer as an apparatus under the conditions of a stirring speed of 1000 rpm and a temperature of 0 ° C. The resulting suspension droplets had an average particle size of about 7 m.

[0192] Next, the suspension was heated to 70 ° C and subjected to polyaddition reaction for 24 hours.

[0193] When the obtained dispersion was observed with an optical microscope, a uniform structure was observed, and the shell layer was observed by dispersing in tetrahydrofuran and extracting the curing agent, and the active hydrogen compound-encapsulated polymer fine particles were observed. I got it.

[0194] The obtained fine particles had an average particle diameter of 7 m and a volume ratio of the curing agent-encapsulating portion was 66%. The amount of isocyanate included was 200% by weight based on the shell. Real column 2-2 (when polyisocyanate is vortex II: no auxiliary polymer)

Dissolved as an active hydrogen compound in 45 g of an aqueous solution obtained by dissolving 450 mg of polyvinyl alcohol as a dispersion stabilizer in water, 2800 mg of isophorone diisocyanate as a polyisocyanate (Wako Pure Chemical Industries, Ltd., 094-03025) Suspended a solution of 250 mg of aliphatic polyamine (Japan Epoxy Resin Co., Ltd., YLH1204) uniformly mixed [0195] The chemical equivalent ratio of the polyisocyanate to the active hydrogen compound is polyisocyanate: active hydrogen compound = 8: 1.

[0196] The suspension was carried out using a homogenizer as an apparatus under the conditions of a stirring speed of 1000 rpm and a temperature of 0 ° C. The obtained suspension droplets had an average particle size of about 8 m.

[0197] Next, the suspension was heated at 70 ° C and subjected to polyaddition reaction for 24 hours.

[0198] When the obtained dispersion was observed with an optical microscope, a uniform structure was observed. By dispersing in tetrahydrofuran and extracting the curing agent, a shell layer was observed, and active hydrogen compound-encapsulated polymer fine particles were obtained. I got it.

[0199] The obtained fine particles had an average particle size of 8 µm and a volume ratio of the curing agent-encapsulating portion was 78%. The amount of isocyanate included was 350% by weight based on the shell.

¾ Example 2-3 (when polyisocyanate is :; power II: no auxiliary polymer used)

Dissolved as an active hydrogen compound in 45 g of an aqueous solution obtained by dissolving 450 mg of polyvinyl alcohol as a dispersion stabilizer in water, 2800 mg of isophorone diisocyanate as a polyisocyanate (Wako Pure Chemical Industries, Ltd., 094-03025) Aliphatic polyamine (Japan Epoxy Resin Co., Ltd., YLH1204) Suspended solution of lOOmg uniformly mixed

[0200] The chemical equivalent ratio of the polyisocyanate to the active hydrogen compound is polyisocyanate: active hydrogen compound = 20: 1.

[0201] The suspension was carried out using a homogenizer as an apparatus under the conditions of a stirring speed of 1000 rpm and a temperature of 0 ° C. The resulting suspension droplets had an average particle size of about 6 m.

[0202] Next, the suspension was heated at 70 ° C and subjected to polyaddition reaction for 24 hours.

[0203] When the obtained dispersion was observed with an optical microscope, a uniform structure was observed, and a shell layer was observed by dispersing in tetrahydrofuran and extracting the curing agent, and active hydrogen compound encapsulated polymer fine particles were observed. I got it.

[0204] The obtained fine particles had an average particle diameter of 6 µm, and the volume ratio of the curing agent-encapsulating portion was 90%. The amount of isocyanate included was 950% by weight based on the shell. Real train 2-4 (when polyisocyanate is vortex II: no auxiliary polymer)

Dissolved as an active hydrogen compound, 1400 mg of isophorone diisocyanate (Wako Pure Chemical Industries, Ltd., 094-03025) as a polyisocyanate into 30 g of an aqueous solution obtained by dissolving 300 mg of polyvinyl alcohol in water as a dispersion stabilizer Suspended a solution of 500 mg of aliphatic polyamine (Japan Epoxy Resin Co., Ltd., YLH1204) uniformly mixed

[0205] The chemical equivalent ratio of the polyisocyanate to the active hydrogen compound is polyisocyanate: active hydrogen compound = 2: 1.

[0206] The suspension was carried out using a homogenizer as an apparatus under the conditions of a stirring speed of 1000 rpm and a temperature of 0 ° C. The resulting suspension droplets had an average particle size of about 4 m.

[0207] Next, the suspension was heated at 70 ° C and subjected to polyaddition reaction for 24 hours.

[0208] When the obtained dispersion was observed with an optical microscope, a uniform structure was observed, and a shell layer was observed by dispersing in tetrahydrofuran and extracting the curing agent, and active hydrogen compound-encapsulated polymer fine particles were observed. I got it.

[0209] The obtained fine particles had an average particle size force of μm, and the volume ratio of the curing agent-encapsulating portion was 33%. The amount of isocyanate included was 50% by weight based on the shell.

¾Example 2-5 (when polyisocyanate is :; power II: no auxiliary polymer used)

30 g of an aqueous solution obtained by dissolving 300 mg of polyvinyl alcohol as a dispersion stabilizer in water was added to Japan Epoxy Resin Co., Ltd., Coronate HX 197 as a polyisocyanate.

5 mg of a modified aliphatic polyamine (Japan Epoxy Resin Co., Ltd., YLH1204) lOOmg as an active hydrogen compound was uniformly mixed and suspended.

[0210] The chemical equivalent ratio of the polyisocyanate to the active hydrogen compound is polyisocyanate: active hydrogen compound = 5: 1.

[0211] The suspension was carried out using a homogenizer as an apparatus under the conditions of a stirring speed of 1000 rpm and a temperature of 0 ° C. The resulting suspension droplets had an average particle size of about 4 m.

[0212] Next, the suspension was heated at 30 ° C and subjected to a polyaddition reaction for 24 hours. [0213] When the obtained dispersion was observed with an optical microscope, a uniform structure was observed, and the shell layer was observed by dispersing in tetrahydrofuran and extracting the curing agent, and the active hydrogen compound-encapsulated polymer fine particles were observed. I got it.

[0214] The obtained fine particles had an average particle size force of μm, and the volume ratio of the curing agent-encapsulating portion was 66%. The amount of isocyanate included was 200% by weight based on the shell. Real train 2-6 (When polyisocyanate is vortex II, auxiliary polymer is not used)

30 g of an aqueous solution obtained by dissolving 300 mg of polyvinyl alcohol as a dispersion stabilizer in water, 1975 mg of methylene diisocyanate (Japan Epoxy Resin Co., Ltd., Millionate MR-200) as polyisocyanate, modified fat as active hydrogen compound A polyamine (Japan Epoxy Resin Co., Ltd., YLH1204) A solution prepared by uniformly mixing lOOmg was suspended.

[0215] The chemical equivalent ratio of the polyisocyanate to the active hydrogen compound is polyisocyanate: active hydrogen compound = 5: 1.

[0216] The suspension was carried out using a homogenizer as an apparatus under the conditions of a stirring speed of 1000 rpm and a temperature of 0 ° C. The resulting suspension droplets had an average particle size of about 5 m.

[0217] Next, the suspension was heated at 30 ° C and subjected to a polyaddition reaction for 24 hours.

[0218] When the obtained dispersion was observed with an optical microscope, a uniform structure was observed, and a shell layer was observed by dispersing in tetrahydrofuran and extracting the curing agent, and active hydrogen compound-encapsulated polymer fine particles were observed. I got it.

[0219] The obtained fine particles had an average particle size of 5 µm and a volume ratio of the curing agent-encapsulating portion was 66%. The amount of isocyanate included was 200% by weight based on the shell. Real train 2-7 (when polyisocyanate is vortex II)

30 g of an aqueous solution obtained by dissolving 300 mg of polyvinyl alcohol as a dispersion stabilizer in water, 1750 mg of isophorone diisocyanate as a polyisocyanate (Wako Pure Chemical Industries, Ltd., 094-03025), dodecane as an active hydrogen compound Diol (Nacalai Testa Co., Ltd., 14204-52) Since 320 mg is poorly soluble, a solution of 3700 mg of tetrahydrofuran (Nacalai Tesque Co., Ltd., 33113) dissolved in 3700 mg is suspended. Let

[0220] The chemical equivalent ratio of the polyisocyanate to the active hydrogen compound is polyisocyanate: active hydrogen compound = 5: 1.

[0221] The suspension was carried out using a homogenizer as an apparatus under the conditions of a stirring speed of 1000 rpm and a temperature of 0 ° C. The resulting suspension droplets had an average particle size of about 4 m.

[0222] Next, the suspension was heated at 30 ° C and subjected to a polyaddition reaction for 24 hours.

[0223] When the obtained dispersion was observed with an optical microscope, a uniform structure was observed, and a shell layer was observed by dispersing in tetrahydrofuran and extracting the curing agent, and active hydrogen compound-encapsulated polymer fine particles were observed. I got it.

[0224] The obtained fine particles had an average particle size force of µm, and the volume ratio of the curing agent-encapsulating portion was 66%. The amount of isocyanate included was 200% by weight based on the shell. Example 2— ί (If the polyisocyanate is too little with a 7k active compound: no auxiliary polymer used)

Polyacetate 450 mg as a dispersion stabilizer dissolved in water 45 5 g, isophorone diisocyanate as polyisocyanate (Wako Pure Chemical Industries, Ltd., 094-03025) 1709 mg, modified as active hydrogen compound Suspended a solution of 1220 mg of aliphatic polyamine (Japan Epoxy Resin Co., Ltd., YLH1204) uniformly mixed

[0225] The chemical equivalent ratio of the polyisocyanate to the active hydrogen compound is polyisocyanate: active hydrogen compound = 1: 1.

[0226] The suspension was carried out using a homogenizer as an apparatus under the conditions of a stirring speed of 1000 rpm and a temperature of 0 ° C. The resulting suspension droplets had an average particle size of about 5 m.

[0227] Next, the suspension was heated at 70 ° C and subjected to polyaddition reaction for 24 hours.

[0228] When the obtained dispersion was observed with an optical microscope, a uniform structure was observed. By dispersing the dispersion in tetrahydrofuran and extracting the curing agent, no shell layer was observed, and the active hydrogen compound capsule polymer The fine particles were obtained. [0229] The obtained fine particles had an average particle diameter of 5 µm, and no hollow portion was observed. Also, the isocyanate was not encapsulated at all.

Example 2_ 2 (If there is too much polyisocyanate in the active hydrogen compound: no auxiliary polymer is used)

Dissolved as an active hydrogen compound, 45 g of an aqueous solution obtained by dissolving 450 mg of polyvinyl alcohol as a dispersion stabilizer in water, 7000 mg of isophorone diisocyanate as a polyisocyanate (Wako Pure Chemical Industries, Ltd., 094-03025) Aliphatic polyamine (Japan Epoxy Resin Co., Ltd., YLH1204) Suspended solution of lOOmg uniformly mixed

[0230] The chemical equivalent ratio of polyisocyanate to active hydrogen compound is polyisocyanate: active hydrogen compound = 50: 1.

[0231] The suspension was carried out using a homogenizer as an apparatus under the conditions of a stirring speed of 1000 rpm and a temperature of 0 ° C. The resulting suspension droplets had an average particle size of about 6 m.

[0232] Next, the suspension was heated at 70 ° C and subjected to polyaddition reaction for 24 hours.

[0233] When the obtained dispersion was observed with an optical microscope, a uniform structure was observed, and a shell layer was observed by dispersing in tetrahydrofuran and extracting the curing agent, and active hydrogen compound-encapsulated polymer fine particles were observed. I got it.

[0234] The obtained fine particles had an average particle diameter of 6 µm, and the volume ratio of the curing agent-encapsulating portion was 96%. The amount of isocyanate included was 2450% by weight based on the shell.

[0235] The product did not form a strong shell layer and could not be obtained in a particulate state in the drying stage.

Actual row 2-8 (when active hydrogen compound is vortex II)

Dissolved as 3 Og of aqueous solution obtained by dissolving 300 mg of polyvinyl alcohol in water as a dispersion stabilizer, 200 mg of isophorone diisocyanate as a polyisocyanate (Wako Pure Chemical Industries, Ltd., 094-03025), modified as an active hydrogen compound Suspended solution of 715mg of aliphatic polyamine (Japan Epoxy Resin Co., Ltd., YLH1204) uniformly mixed [0236] The chemical equivalent ratio of the polyisocyanate to the active hydrogen compound is polyisocyanate: active hydrogen compound = 1: 5.

[0237] The suspension was carried out using a homogenizer as an apparatus under the conditions of a stirring speed of 1000 rpm and a temperature of 0 ° C. The resulting suspension droplets had an average particle size of about 7 m.

[0238] Next, the suspension was heated at 70 ° C and subjected to polyaddition reaction for 24 hours.

[0239] When the obtained dispersion was observed with an optical microscope, a uniform structure was observed. A shell layer was observed by dispersing in tetrahydrofuran and extracting the curing agent, and active hydrogen compound encapsulated polymer fine particles were observed. I got it.

[0240] The obtained fine particles had an average particle diameter of 7 m, and the volume ratio of the curing agent-encapsulating portion was 66%. The encapsulated amount of the active hydrogen compound was 200% by weight with respect to the shell.

1-component isocyanine scented adhesive composition Example of composition test, test Polyisocyanate-containing capsule polymer fine particles obtained in Example 1 and modified aliphatic amine (Japan Epoxy Resin Co., Ltd.) YLH1204) was mixed in such a way that the chemical equivalent ratio was 1: 1 (polyisocyanate: capsule active hydrogen compound).

[0241] Two aluminum plates of 10 mm X 50 mm X 1 mm were used, a one-part adhesive was applied with an adhesion area of lcm ² and the two aluminum plates were pressed in a vise.

[0242] A tensile shear test was performed using an autograph (manufactured by Shimadzu Corp.) after standing at room temperature or 70 ° C for 1 day. Those left at room temperature did not show adhesiveness, but those left at 70 ° C were firmly bonded and showed an adhesive strength of about 190 N / cm ² . It is considered that polyisocyanate and polyamine released by the destruction of fine particles were cured by polyaddition reaction by heating.

[0243] From this, it was determined that the isocyanate resin composition containing the fine particles containing the active hydrogen compound of the present invention could be used as a one-component adhesive.

The fine particles obtained in Comparative Example 2 and the modified aliphatic amine (Japan Epoxy Resin Co., Ltd., YLH1204) were mixed with an equivalence ratio of 1: 1 (polyisocyanate: capsule active hydrogen compound). ) To obtain a one-pack type adhesive. The adhesive strength of this adhesive was evaluated in the same manner as in Formulation Example 1, but it did not show any adhesive strength.

Claims

The scope of the claims

[I] Shell and hollow part force Hollow fine part of hollow fine particles encapsulated with epoxy resin hardener, and shell force is substantially the same kind of hardener and epoxy hardener as encapsulated hardener. Curing agent-encapsulated fine particles made of cured epoxy resin obtained by reaction with fat.

2. The fine particles according to claim 1, wherein the epoxy resin is a bi- to 6-functional epoxy resin.

[3] The fine particles according to [1], wherein the amount of the curing agent is 50 to 500% by weight based on the shell.

[4] The fine particles according to claim 1, wherein the average particle size is 0.1 l to 50 _i um.

[5] The fine particles according to claim 1, wherein the volume ratio R of the curing agent-containing portion calculated according to the following formula is 10 to 80%.

R (%) = (rh / rp) ³ X 100

(Where rh is the radius of the hardener-containing portion of the microparticle, and rp is the radius of the microparticle.)

[6] The fine particle according to claim 1, wherein the crushing limit load is 1 to: LOOmN.

[7] A curing agent for a one-pack type epoxy resin adhesive containing the fine particles according to claim 1.

[8] Use of the fine particles according to claim 1 as a curing agent for a one-pack type epoxy resin adhesive.

[9] A method for producing fine particles in which a hollow portion of a hollow fine particle having a shell and a hollow partial force is encapsulated with an epoxy resin hardener,

Auxiliary polymer or co-solvent: interfacial tension _(Ί ^P between compatibility with curing Engineering epoxy榭脂obtained by reacting epoxy榭脂and hardener Teigukatsu, the auxiliary polymer or co-solvent and water ) (mN / m) and cured epoxy榭脂and in relation to the interfacial tension ^{(γ q) (mN / m} ) between water, gamma ^[rho satisfy polymer or solvent ≥ gamma ¹¹

10. The production method according to claim 9, wherein the epoxy resin is a bi- to 6-functional epoxy resin.

[II] One-pack type epoxy resin adhesive composition comprising the fine particles according to claim 1 and epoxy resin object.

[12] A step of placing the composition according to claim 11 between a pair of adherends, a step of releasing the hardener from the fine particle sheller by pressing the adherends, an epoxy resin and a hardener And a step of adhering the adherends to each other by a crosslinking reaction.

[13] A step of placing the fine particles according to claim 1 and an epoxy resin in a mixed state between a pair of adherends, and a step of releasing the curing agent from the fine particle shellers by pressing the adherends together. A method for adhering an adherend, comprising a step of causing a cross-linking reaction between an epoxy resin and a curing agent to bond the adherends.

[14] A fine particle in which an active hydrogen compound or polyisocyanate selected from the group consisting of polyol, polyamine, and polythiol force is encapsulated in a hollow portion of a hollow fine particle having a shell and a hollow partial force, Isocyanate resin-constituting component-enclosed microparticles substantially comprising an isocyanate resin obtained by polyaddition reaction of a component of the same type as the included component and a polyisocyanate or the active hydrogen compound.

[15] The fine particles according to claim 14, wherein the inclusion amount of the isocyanate component is 50 to 1500% by weight based on the shell.

[16] The fine particles according to [14], having an average particle diameter of 0.1 to 50 m.

[17] The fine particle according to [14], wherein the volume ratio scale of the isocyanate containing component component calculated in accordance with the following formula is 30 to 95%.

R (%) = (rh / rp) ³ X 100

[18] The fine particle according to [14], wherein an active hydrogen compound selected from the group consisting of a polyol, a polyamine, and a polythiol force is encapsulated.

[19] The fine particles according to [14], wherein the polyisocyanate is encapsulated.

[20] A one-component isocyanate resin component comprising the fine particles according to claim 14.

[21] Use of the fine particles according to claim 14 as a one-component isocyanate resin component.

[22] A method for producing fine particles in which an isocyanate resin component is encapsulated in a hollow portion of a hollow fine particle such as a shell and a hollow portion cover, A mixture of a polyisocyanate and an active hydrogen compound selected from the group consisting of polyol, polyamine, and polythiol in an aqueous dispersion stabilizer solution, wherein the active hydrogen compound is mixed in a polyisocyanate. A first step of dispersing a mixture having a chemical equivalent ratio of 2 to 25 or a polyisocyanate mixture ratio of 2 to 25 in terms of a chemical equivalent ratio to the active hydrogen compound, and a polyisocyanate And a second step of subjecting the active hydrogen compound and the active hydrogen compound to a double caloric reaction.

[23] The mixture according to claim 22, wherein the mixture dispersed in the aqueous solution of the dispersion stabilizer contains an auxiliary polymer or auxiliary solvent having the following properties in addition to the polyisocyanate and the active hydrogen compound. the method of.

Auxiliary polymer or auxiliary solvent: low compatibility with isocyanate resin obtained by polyaddition reaction of polyisocyanate and active hydrogen compound, and interfacial tension between auxiliary polymer or auxiliary solvent and water ( A polymer or solvent satisfying the condition of γ ^χ ≥ γ ^y with respect to the relationship between γ ^x ) (mN / m) and the interfacial tension (γ ^y ) (mN / m) between isocyanate and water.

[24] A one-component polyurethane adhesive composition comprising the fine particles according to claim 18 and a polyisocyanate.

[25] A one-component polyurethane adhesive composition comprising the fine particles according to claim 19 and an active hydrogen compound selected from the group consisting of polyol, polyamine, and polythiol.

[26] A step of placing the composition according to claim 24 between a pair of adherends, a step of releasing the active hydrogen compound from the fine particle sheller by pressing the adherends, an active hydrogen compound, A method for adhering an adherend, comprising a step of adhering the adherends by polyaddition reaction with a polyisocyanate.

[27] A step of mixing the fine particles according to claim 18 and a polyisocyanate between a pair of adherends, and a step of releasing the fine particle shell force active hydrogen compound by pressing the adherends together. A method for adhering an adherend, comprising a step of subjecting the active hydrogen compound and polyisocyanate to a polyaddition reaction to adhere between the adherends.

[28] The step of placing the composition according to claim 25 between a pair of adherends, the step of releasing the polyisocyanate by pressing the adherends together to release the polyisocyanate, the polyisocyanate and the activity And a step of adhering between the adherends by a polyaddition reaction with a hydrogen compound. Bonding method of objects.

A step of mixing the fine particles according to claim 19 and an active hydrogen compound between a pair of adherends, a step of releasing the fine particle shell force polyisocyanate by pressing the adherends together, A method of adhering an adherend, comprising a step of subjecting a cyanate and an active hydrogen compound to a polyaddition reaction to adhere between the adherends.